Grease-setting agent



Patented Apr. 18, 1939 r oFFic GREASE- SETTING AGENT Torsten Hasselstrom, Savannah, Ga., assignor to' G. & A. Laboratories, Savannah, Ga., a corporation of Georgia No Drawing. Original application March 24,

1937, Serial No. 70,671.

Divided and this application August 26, 1937, Serial No. 161,165

2 Claims.

This invention relates to an improved detergent, wetting and grease-setting agent and process of producing the same.

Many detergents and wetting agents are known, for example, soaps, sulfonated castor oil, sulfated higher fatty alcohols, sulfonated higher fatty acids, etc. Of these, soaps suffer from the disadvantage of being precipitated from their aqueous solutions by the electrolytes in hard waters, 0 particularly by waters carrying calcium compounds, and the sulfated alcohols of the higher fatty acids and the sulfonated higher fatty acids suffer from the disadvantage of high cost of the higher fatty alcohol used, so that their use in ,5 trade has been severely limited.

The product in accordance with my invention possesses superior detergent and wetting powers, in comparison with many of those now used in various industries, as, for example, in the manu- 10 facture of soap, the textile and tanning industries, and many others, is economical to manufacture, requires no complicated separation and isolation of the material to be sulfonated, and may be made by a very simple sulfonation process and apparatus. My product is not precipitated by calcium salts contained in hard waters, and is non-hydrolyzable by alkali or acid under practical conditions of use.

Broadly speaking my invention comprises the n product of the sulfonation of pseudopimaric acid, for example, prepared in accordance with the process disclosed in application for United States Letters Patent, Serial No. 675,976, filed June 15, 1933, entitled A new rosin acid and process of producing the same, in accordance with which rosin oil having an appreciable resin acid content, say at least about five per cent, or a product obtained from rosin by suitable heat treatment (with or without distillation), such as a rosin 0 known in the trade as a heat-treated or partially distilled rosin, is extracted with an aqueous solution of an alkali, which is preferably caustic soda or caustic potash. The extraction is carried out preferably. by thoroughly mixing the raw material and the alkaline solution in an appropriate manner, as by stirring or agitation, and is continued until practically complete saponification is'accomplished. In order to break up any emulsion and to facilitate the separation of the mixture into two layers, some methanol or other suitable solvent is added just prior to the termination of the agitation. Upon standing, the mixture then separates into two'layers, the upper-consisting mainly of unsaponifiable material and the lower one containing the alkali pseudopimarate in alkaline solution. This lower layer is then drawn off, acidified with a dilute mineral acid, such as hydrochloric acid or sulfuric acid, or by the addition of a suitable acid salt, such as nitre cake. This acidification precipitates the novel acid, called pseudopimaric acid, as a viscous, sticky mass, which is collected by agglomeration and then removed. It is then pressed to free it as much as possible from adhering mother liquor, and is washed thoroughly with water until substantially free from all water-soluble bontaminants. The crude acid is then dried in any suitable way.

The pseudopimaric acid so produced melts at about SQ-71 C., while the partially purified pseudopimaric acid melts at about 169-181 C., has an optical angle of rotation [a119, of about +25 to +50, and when more fully refined melts at 195.5 to 198 C. (corrected), has an optical angle of rotation, [(2:11), of about +0.33 and an elementary composition which corresponds approximately to the formula CzoHsoOz. As the properties of the new acid are not identicaLwith either the abietic or the pimaric types of acids, it

- is called pseudopimaric acid.

More specifically my invention comprises sulfonation by treatment by concentrated sulfuric acid of pseudopimaric acid or of mixtures containing pseudopimaric acid, such, for example, as result from suitable heat-treatment of wood and/or gum rosin, if desired in a suitable solvent attacked or unattacked by concentrated sulfuric acid, e. g. carbon tetrachloride, liquid sulfur di-. oxide, petroleum distillates, saturated and/or un-' saturated hydrocarbons, preferably of the aromatic and/or hydroaromatic series, although I may employ unsaturated aliphatic hydrocarbons,

. or mixtures thereof.

As sulfonating agent I preferably employ sulfuric acid of specific gravity about 1.84, although I may employ somewhat lower or somewhat higher strengths, even to fuming sulfuric acid, or chlorosulfonic acid or sulfur trioxide as the sulfonating agent.

' Example I and. 250 parts by weight of sulfuric acid sp. r. 1.84 were mixed at about 5 to +5,C., stirred for about 20 minutes, then poured onto cracked ice. The brownish precipitate was filtered out,

washed with cold water until the washings clouded when mixed with the original liquor, and the washed precipitate then extracted three times with boiling water, leaving a brownish, insoluble semi-solid resin. The hot aqueous extracts, on cooling, deposited crystalline sulfonic acid in a yield of 25.5 parts by weight, which, after repeated crystallization from glacial acetic acid, melted with decomposition at about 223-224 C. The brownish insoluble semi-solid resin amounted to parts by weight. When an acetone solution of this by-product was allowed to stand for several days, it separated a colorless, crystalline solid, which, after recrystallization from suitable solvents, melted at about 131-132 0. Instead of the partially refined pseudopimaric acid used in this example, a pseudopimaric acid of greater or less purity may be employed with consequent variation in the yields of the sulfonic acid.

Example II As a further example of the carrying out of my process, 1200 parts by weight of a finely pulverized product, rich in pseudopimaric acid, obtained by suitable destructive distillation of wood and/or gum rosin, followed by removal of abietenes, etc., by fractional distillation under reduced pressure were mixed with 2400 parts by weight of sulfuric acid sp. gr. 1.84, and the mixture agitated for a suitable time at 10-35 C., then treated as in Example I. The crude product from this reaction was extracted twice with boiling water and allowed to stand to crystallize. A sulfonic acid of lighter color than in Example I was obtained, M. P. 223-4 0. with decomposition, [m]D=+62.63, yield 465 parts by weight, and also a dark noncrystalline sulfonic acid, whose sodium salt in aqueous solution behaved like a soap, of yield of 190 parts by weight.

Example III As a further example of the carrying out of my process, 400 parts by weight of a finely pulverized product rich in pseudopimaric acid, and obtained by suitable destructive distillation of wood rosinv Example IV As a further example of the carrying out of my process in the presence of a suitable solvent, 9. mixture of 100 parts of steam-distilled rosin oil, rich in pseudopimaric acid, and containing a total of up to about 70% of resin acids calculated as C20H30O2, with 200 parts of concentrated sulfuric acid of a sp. gr. of about 1.84 was agitated for a suitable length of time at a temperature of about 5 C. to about (2., and the crude sulfonation product so obtained worked up as in Example 11. a

My sulfonic acid product will be found variously adaptable to uses as an improved detergent and wetting out agent, e. g. in the scouring of textiles, as a soap assistant, etc.

I may prepare the neutral or acid, alkali, or alkaline earth salts, or salts of organic bases, e. g. of ethanolamine of my sulfonic acid product and such are also variously adaptable to uses in an improved detergent and wetting out agent.

The brownish, insoluble semi-solid resin material separated from the sulfonic acid, as shown, for example, in Example I, I have found useful as a grease-setting agent, e. g. in the manufacture of cup grease, solid oils, and the like.

This application constitutes a division of my application Serial No. 70,671, flied by me March 24, 1936, for Detergent and wetting agent and process of producing the same and now issued as Patent No. 2,121,032 of June 21, 1938.

What I claim and desire to protect by Letters Patent is:

1. As a grease-setting agent, the brownish, insoluble, semi-solid resin obtained by treating a material from the group consisting of pseudopimaric acid and mixtures containing pseudopimaric acid with a sulfonating agent, and-removing by hot aqueous extraction the water soluble sulfonic acid.

2. As a grease-setting agent, the brownish, insoluble, semi-solid resin obtained by treating pseudopimaric acid with sulfuric acid of density about 1.84 and removing byhot aqueous extraction the water-soluble sulfonic acid.

'roRs'rEN mssmsmou. 

